DE1264141B - Low-smoke burning diesel oil containing an oil-soluble metal compound - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

GERMAN

PATENT OFFICE

EDITORIAL

Int. CL:

ClOl

German class: 46a6-7

Number: 1264 141

File number: L 50374IV d / 46 a6

Filing date: April 2, 1965

Open date: March 21, 1968

In the work of diesel engines, the incomplete combustion of diesel oil is a difficult one Problem. The incomplete combustion of the diesel oil causes excessive wear on the machine parts and reduces the efficiency of the engine. It also leads to the formation of black exhaust smoke, especially when the engine accelerates rapidly. The one formed by a diesel engine black smoke pollutes the air.

US Pat. No. 3,124,433 describes diesel oils which contain an organometallic compound preferably an organic lead compound, such as tetraethyl lead, and a wetting and dispersing agent, preferably an oil-soluble alkali or alkaline earth metal sulfonate contain. Draw such diesels are characterized by improved combustion properties and reduced formation of black smoke.

Diesel oils known from the German Auslegeschrift 1071867 should burn with particularly little smoke, the two or more sulfonates of metals of Groups II, IV, V, IVb or VIII of the Periodic System of elements included, the smoke development in particular by a combination of tin and lead sulfonates should be greatly reduced.

However, normal sulfonic acid salts are regularly detergents and act as a detergent in oil-water systems Emulsifiers. Furthermore, the use of many organometallic compounds is prohibited, in particular that of lead, because of its toxicity and / or the toxicity of the resulting from it when burned Products that get into the air with the exhaust gases.

Since, as has been established, the smoke development is also the best known in this regard Diesel oils, namely those that contain a combination of tin sulphonate and lead sulphonate, is still unsatisfactorily high, it is desirable to consider other less harmful ones the improvement of the combustion properties and the other properties of diesel oils to use additives that do not have a detrimental effect.

The invention relates to a low-smoke burning, oil-soluble metal compound containing Diesel oil, which is characterized in that it contains 0.1 to 5 percent by weight of an oil-soluble, contains overbased metal salt obtained by treating a mixture of

a) either one or more alkylated phenols with at least about 6 aliphatic carbons

Low-smoke burning, an oil-soluble one
Diesel oil containing metal compounds

Applicant:

The Lubrizol Corporation,
Cleveland, Ohio (V. St. A.)

Representative:

Dr. E. Jung and Dr. V. Vossius, Patent Attorneys, 8000 Munich 23, Siegesstr. 26th

Named as inventor:
William Monroe Le Suer,
Cleveland, Ohio (V. St. A.)

Claimed priority:

V. St. v. America April 6, 1964 (357 787)

atoms or from a mixture of a phenol and one or more polar compounds with at least about 12 aliphatic carbon atoms from the group of esters of aliphatic carboxylic acids, alcohol, sulphurized Sperm oil, sulfoxides, amines and condensation products of amines with lower aliphatic Aldehydes or with carboxylic acids and

b) at least about 1 equivalent of an alkali or alkaline earth metal oxide or hydroxide

with carbon dioxide, optionally in the presence of a mineral oil as a diluent and optionally in the presence of water.
The overbased metal salts used as additives in the diesel oils according to the invention are characterized by a pronounced degree of basicity, as determined by the so-called reflux basicity method. In this method, a solution of the metal salt in a solvent mixture of toluene-isopropanol-water (volume ratio 49: 49: 0.5) and a measured excess of aqueous hydrochloric acid is refluxed and the excess acid is back-titrated with potassium hydroxide solution of known normality. The basicity of the metal salt is expressed in milligrams of KOH, which is equivalent to 1 g of the compound. In the description, the one after this

809 519/531

3 4

Working method specific basicity as »reflux bases- derive. Examples of esters are methyl stearate, number «. The in the invention cyclohexyl oleate, sorbitan monooleate, butyl stearate, Metal salts used in diesel oils have an ethyl laurate, allyl myristate, ethyl palmitate, the diester The reflux base number of at least about 10 of ethylene glycol and stearic acid and the tetra-such Overbased oil-soluble metal salts were esters of pentaerythritol with oleic acid. Esters of im the fatty acids or acid mixtures available in very small quantities of not more than 0.06 g weight percent already diesel oils are used as stabilizers because of their easy accessibility and low antioxidants and agents for preventing costs are particularly preferred. This includes both Blockage of the fuel filter added (see, for example, sperm oil, tall oil, methyl ester and behenyl USA.-Patents 2 781403 and 3 031284). io ester of tall oil acid.

In these very small amounts their smoking examples of alcohols, which in admixture with formation-reducing effect, however, are so slight, the phenol for the production of the overbased metal, that it was not noticed. Salts that can be used are dodecyl alcohol, for component a) either one or octadecyl alcohol, sperm alcohol (obtained by several alkylated phenols or a mixture of a ¹ S hydrolysis of sperm oil), behenyl alcohol, oleyl phenol and one or more of the following alcohol and "oxo" alcohols, as used by the oxo bonds: esters of an aliphatic carbon reaction of an olefin with at least 12 carbon acids, alcohols, sulphurized sperm oil, sulfoxides, atoms with carbon monoxide and hydrogen, amines and condensation products of an amine are obtained with. You can store up to 30 aliphatic carbon Low aliphatic aldehydes or carbon atoms or ^ao contain more.

acids. The alkylated phenols are intended to be at least examples of sulfoxides which have about 6 aliphatic carbon atoms in a mixture. If one or more salts can be used with the phenol for the production of the overbased metal on the aromatic nucleus, they are dodecylmethylsulfoxide, carry alkyl radicals. Examples of the alkylated phenols Didodecylsulfoxyd, Hexyloctadecylsulfoxyd, Dibehesind hexylphenol, heptylphenol, dodecylphenol, di- ² 5 nylsulfoxyd and Dioctadecylsulfoxyd. Hexylphenol / Diisopropylphenol / Tributylphenol / Dido amines, which are substituted in a mixture with the phenol to form decylphenol, octadecylphenol, dioctylphenol, useful with the preparation of the overbased metal salts. They include, for example, dodecylamine, substituted phenol, cyclohexylphenol, dodecyl-3 ° didodecylamine, N-methyldodecylamine, N-benzyloctacyclohexylphenol and behenylphenol. In some cases decylamine, dicyclohexylamine, tridecylamine, N-butyl can be a polar group, such as a halogen atom, a laurylamine and Ν, Ν-dimethylpentadecylamine. These include nitro or alkoxy groups in the alkyl radical or the polyamines, such as N-octadecylpropylene aromatic nucleus of the alkylated phenols, diaroin, N-decylpropylenediamine, tridecyl-substituted. Bisphenols and other alkylated hydroxy- 35 diethylenetriamine and octyl-substituted tetraethylene aromatic compounds such as alkylated naphthols, pentamine. The preferred polyamines are N-alkyl are also suitable. The preferred alkylated substituted alkylene amines such as substituted ethylene phenols are the mono- and di-alkylated phenols, diamines, trimethylene diamines, tetramethylene diamines, in which the alkyl substituent contains about 6 to 200 carbon triethylene tetramines, pentaethylene hexamines and an atomic atom. 4 ° other polyalkylenepolyamines. The alkyl groups of such As indicated above can also contain a mixture of N-alkyl substituted polyamines containing from about 12 to about a phenol and one or more polar 30 carbon atoms. Other polyamines, compounds can be used. The phenol useful in such as acylated imidazolines having an acyl group on admixture may be any of the one or some of the amino groups, also alkylated phenols described above or such are useful. A typical example is the reaction being which has no alkyl radical or a product of 1 mole of oleic acid with 1 mole of triethylene or more lower alkyl radicals, ie with less tetramine. Still other amines useful here are than 6 carbon atoms. Therefore, in addition to the examples given above of the alkyl phenols in which the alkyl radical has up to about 6 carbon atoms, other hydroxyalkylamines, including polyamines, can be used in such a mixture. Such hydroxyalkylamines are made up of bare phenols: phenol, naphthol, cresol, pyrenic reaction of an epoxide such as ethylene oxide, propylene catechol, isopropylphenol, diethylphenol, «-methyl oxide or epichlorohydrin with dodecylamine, N-octass-naphthol, ß-butyl-oc- formed naphthol or 4,4'-methylenecyltrimethylenediamine or didecylamine, bis-phenol. Condensation products of the above-mentioned amines The 55 with a lower aliphatic aldehyde with less polar compounds which can be used in a mixture with the phenol should also contain at least about 12 as about 6 carbon atoms in the carbon atoms and can be mixed with the phenol to produce the invention Mixture of esters of aliphatic according to used overbased metal salts carboxylic acids, alcohols, sulfoxides, amines and usable.

Condensation products of an amine and a never- ^6o Examples of preferred aldehydes are form-

their aliphatic aldehydes. The esters aldehyde (paraformaldehyde or aqueous formalin),

Phatic carboxylic acids are preferably esters of acetaldehyde, propionaldehyde and butyraldehyde, The

Fatty acids having at least about 12 carbon atoms, condensation products are easily obtained by

usually up to about 30 carbon atoms in one mole of the amine with about 0.5 to about 5 moles

Fatty acid residue. On the other hand, the ester residue can mix ⁶ 5 of the aldehyde and then the mixture up

from a lower alkyl group such as methyl, a temperature of about 50 to 250 ° C or higher

Ethyl or propyl group, or heated by a higher. If the amine or aldehyde is a solid

Is an alkyl group with up to about 30 carbon atoms, the condensation is best

5 6

was a diluent such as mineral oil, xylene, number hydroxyl groups in the molecule; The equivalent benzene, heavy gasoline, chlorobenzene or a weight of a sulfoxide is determined by the inert solvent used. The number of sulfoxide residues in the molecule; The equivalent densation is determined by the presence of a small weight of an amine is determined by the number of amino amounts, at least about 0.01% ^and usually 5 groups in the molecule; and the equivalent of less than 10 percent by weight of the aldehyde, one of the condensation product of an amine and basic catalyst, such as an alkali or earth, a lower aldehyde is determined by the alkali metal hydroxide, e.g. sodium hydroxide, number of nitrogen atoms, which differ from the potassium hydroxide, calcium hydroxide or derive barium amine. For example, the equivalent hydroxide is promoted in the reaction mixture. The exact ¹⁰ weight of sperm oil its molecular weight (the nature of the condensation products is not known. Is correct by its saponification equivalent); the equi-The condensation products which are obtained from a valent weight of the oleyl alcohol is its molecular mixture of 2 to 4 moles of formaldehyde and 1 mole of a weight; the equivalent weight of an N-alkylalkylene-N-alkylalkylene diamine in which diamines is half its molecular weight; that the alkyl radical has about 12 to 30 carbon atoms and 15 equivalent weight of the distearyl ester of ethylene; the alkylene group has 2 to 4 carbon atoms, glycol is half its molecular weight; these are particularly useful. The equivalent weight of heptylphenol is its mole. For component b) comes the lithium, kular weight; the equivalent weight of 2,2'-di-sodium, potassium, magnesium, calcium, strondecyl-4,4'-methylene-bis-phenol is half of its tium and barium oxides and hydroxides in question. 20 molecular weight; the equivalent weight of di- The calcium and barium oxides and hydroxides are dodecyl sulfoxide is its molecular weight; which is particularly preferred because the equivalent weight of the condensation product of products derived therefrom are particularly effective additives for diesel N-alkyl tetraethylene pentamine with an aldehyde is oils. The relative proportions of the phenol one fifth of its molecular weight; the equivalent to the polar compound or the polar weight of an alkali metal hydroxide is the molar bonds of which in the mixture vary from about 0.1 to kular weight; the equivalent weight of one alkali-10 equivalents of the phenol per equivalent of the poly-metal oxide is half its molecular weight; ren connection. In most cases that and the equivalent weight of an alkaline earth metal oxide mixture contains from about 0.2 to about 5 equivalents of the phenol or hydroxide is half its molecular weight per equivalent of the polar compound. 30 weight.

For the preparation of the overbased metal salts, if component a) is a mixture of one which is used as additives in the diesel phenol according to the invention and a polar compound, the oils are useful, components a) are relative amounts of component b) for compound b ) were mixed together, and the mixture is component a) in relation to the total number of Äquimit carbon dioxide at a temperature of minde- 35 valent of the phenol and of the polar compound at least about 5O ⁰ C, preferably from 80 to 25O ⁰ C, mixture. For example, when dealing with the ratio of equivalents. The upper temperature limit is determined by component b) to component a) 2: 1 is the decomposition point of the reaction mixture and component a) is a mixture of a phenol. The carbonization is preferably carried out in proportions of a polar compound in the presence of a diluent. This 40 which corresponds to a ratio of equivalents of 1: 4 is usually a liquid solvent in which the reaction mixture contains 1 equivalent of at least one of the reactants or the valent of a phenol, 4 equivalents of a polar product is soluble. Suitable solvents for the compound and 10 equivalents of an alkali or sen purpose are benzene, toluene, chlorobenzene, heavy alkaline earth metal oxide or hydroxide.
petrol, dodecane, xylene and mineral oil. At least 45 In the carbonization stage, the mixture is one equivalent of component b) is used per equivalent of component a) and component b) both in component a). There appears to be no upper presence, and in the absence of a dilution limit, the proportion of solvents useful in the process is usually a heterogeneous mixture. To exist metal connection. For practical reasons, however, as the carbonization progresses, the 50 component b) used in the process is dissolved in the organic phase, the proportion of metal compound rarely 25 equivalents each and the carbonized product finally becomes one equivalent of the phenol or the homogeneous phenol-containing product Mass, which in hydrocarbon solution mixture. A larger amount of the metal compounds, such as benzene, xylene or mineral oil, easily soluble can be used, but this does not appear to be borrowed. The mechanism of formation of the homogeneous offer particular advantages. In most cases 55 product is unknown. However, it is assumed that about 1.5 to about 15 equivalents of the men are used that the carbonization of component b) component b) per equivalent of component a). is converted into a carbonate or bicarbonate, the equivalent weight of component a) is which with component a) forms a homogeneous complex depending on the number of functional groups. In most cases it is not in the molecule, and the equivalent weight of the component is required, that the total component b) in the process mixture depends on the valency of the metal and component b) present by carbonization of the number of metal residues in the molecule. So it is necessary to convert in order to form a soluble homogeneous one the equivalent weight of a phenol by the number of product. Such a product is often determined to contain hydroxyl groups which are bonded to the aroot, if only 75% of component b) carbonized, matic core; the equivalent weight are 65. The expression "basic metal compound" of a carboxylic acid ester is determined by the number of times the homogeneous carbonized product is characterized without ester groups in the molecule; the equivalent - a special reference to the degree of reweighting of an alcohol is determined by the conversion of component b) through carbonization.

7 8

The following are instructions for the preparation of acids used is such that 1 equivalent for

given some overbased metal salts, the diesel - each 2 equivalents of the amine mixture used

oils can be incorporated. available. The reaction is exothermic. That

Other manufacturing processes are in the USA. Mixture is blown with nitrogen while one

Patents 2,989,463 and 2,971,014 included. ^{5 it heated to 240 0} C in 4.5 hours and then more

Hold at this temperature for 2 hours for the production of these overbased metal salts. Water will

no protection is claimed here. collected as a distillate. The residue is at

A. A mixture of 630 g (2 equivalents) of a 170 to 180 ° C within a period of 2 hours rosin amine (essentially composed of dehydrode with 140 parts of ethylene oxide, while consisting of abietylamine) with a nitrogen content io one nitrogen through the Reaction mixture bubbled from 44% and 245 g (1.2 equivalents) heptylpheiiol leaves. The reaction mixture is then 15 minutes with a hydroxyl content of 8.3% is blown to 9O ⁰ C with nitrogen and containing 940 parts of xylene to heated and then with 230 g (3 equivalents) of barium a solution diluted 24% xylene, oxide mixed at 90 to 14O ⁰ C. The mixture is blown with nitrogen at ^{140 °} C. The resulting solution has a nitrogen. 600 g of the mixture 15 content of 5.4% and a base number of 82. The are diluted with 400 g of mineral oil and filtered. pH value is 4, which indicates the presence of free The filtrate is blown with carbon dioxide, indicating with amino groups. ^ A portion of the above benzene is diluted, refluxed, the de-xylene solution (789 g, 3 equivalents of nitrogen) is removed from benzene heated, mixed with xylene and filtered to 150 ° C / 2mm Hg to distill off xylene. The filtrate, a 20% xylene solution of the 20 heated and then with heptylphenol __ (with a Hy product, has a barium sulfate ash content of hydroxyl content of 8.3%; 367 g, 1.8 equivalents) ^ ver-25.1%> a Nitrogen content of 2% and a back mix. To this mixture are added 345 g (4.5 equi-flow base number of 119 valents) barium oxide in small proportions at 90 to

B. An amine-aldehyde condensation product is added St. ^0C. The mixture obtained 2.5 hours as follows: formaldehyde (420 g, 14 mol) 25 90 to 120 ⁰ C and heated with carbon dioxide 1.75 Stunwird in small portions to a mixture of the blown. It is diluted with 130 g xylene, and N-Octadecylpropylendiamin (1392 g, 4 mole), micro then heated 3.5 hours at 150 ⁰ C. Then mineral oil (3000 g), water (200 g) and calcium hydroxide is diluted with 20% of its weight xylene and filtered (42 g, condensation catalyst) under reflux. The filtrate has a barium sulfate ash ^{temperature of 100 to 105 °} C. given. The addition content of 33.2%> a nitrogen content of 3.52% rate of formaldehyde is such that and a reflux base number of 134, excessive foaming is avoided. The mixture E. To a mixture of 408 g (2 equivalents) is refluxed for 1 hour, then heptylphenol with a hydroxyl content of 8.3% is slowly heated to 155 ° C and with nitrogen for 2 hours and 264 g of xylene are added 383 g (5 equivalents) 150 to 155 ⁰ C blown in order to remove all volatile constituents 35 barium oxide in small portions at 85 to 100 ⁰ C. Then the product is fil- added. 6 g of water are added. The Gates. The filtrate, 93% of the theoretical yield, is mixed carbonized at 100 to 130 ° C and then a 65.4% oil solution of the amine-aldehyde is filtered. The filtrate is heated to 100 ° C condensation product having a nitrogen content and then with xylene to a 25% xylene solution of 2.4% ig ^s · A portion (1850 g, 3.2 equivalents diluted 40th This solution has a nitrogen Bariumsulfatasche) is mixed with 185 g of heptylphenol (0.97 equivalents of 41% and a reflux base number of 137 valents), 1485 g of mineral oil and 1060 g of 90% F. A 65.4% oil solution of the amine-aldehyde pure barium oxide (12 , 6 equivalents) were mixed, and the condensation product of B (g 1400 2.4 Äquivaauf heated 7O ⁰ C, within a period of lente), heptylphenol (140 g, 0,73 eq) and 1 hour are employed at 70 to 100 ° C 500 g of water 45 barium oxide (368 g, 4.78 equivalents) are added to 70 ° C. The mixture is heated to 110 bis for 4.75 hours. Within a period of 1 hour 115 ⁰ C and then heated to 150 ° C. Thereafter, it will be added at 70 to 100 ⁰ C 250 g of water, carbonized at 140 to 15O ⁰ C and filtered. The mixture is boiled for 4 hours at 110 to 115 ° C under filtrate is a 57.8% i§ ^e oil solution of the overbased reflux and then heated to 150 to 150 metal salt with a nitrogen content of 0.87% 50 155 ° C for 30 minutes. It is then blown at 140 to 150 ^° C. with a barium sulfate ash content of 29.5% carbon dioxide and filtered. The filtrate is

C. A mixture of 423 g (1 equivalent) of sperm oil, a 47% strength oil solution of the desired product, 123 g (0.602 equivalents) of heptylphenol, 1214 g of Mi- and has a barium sulfate ash content of 27.8 ⁰ _{I 0} , mineral oil and 452 g of water is treated at 70 ° C with 612 g a nitrogen content of 1.65% and a reflux (8 equivalents) barium oxide. The base number is 78.

mix is 1 hour at the reflux temperature and G. The procedure of F is repeated with

then stirred at 150 ⁰ C, while in the mixture with the exception that 1091 g of barium oxide (14.2 equiv

introduces carbon dioxide below its surface. The valente) can be used and that one 1041 g

carbonized product is filtered and the filtrate possesses mineral oil prior to carbonization to the reaction a sulfated ash content of 35%. 60 mixture added. The product is a 50%

D. A partially acylated polyamine is an oil solution and has a barium sulfate ash content measured: a mixture (565 parts by weight) of 36.1%, a nitrogen content of 0.83% and of an alkylene amine mixture, which from triethylene has a reflux base number of 168.

tetramine and diethylenetriamine in the weight ratio- H. A mixture of with polyisobutene from MoIe-

nis 3: 1 is, at 20 to 80 ° C to a ge 65 kular weight 300 substituted phenol with a

mixed equivalent amounts of a naphthenic acid with a hydroxyl content of 3.76% (200 g, 0.44 equivalents)

an acid number of 180 (1270 parts) and oleic acid and heptylphenol with a hydroxyl content of

(1110 parts) given. The total amount of both 8.3% (200 g, 0.98 equivalents) and 200 g of xylene will be

ίο

heated to 80 ^{° C.} Then there is barium oxide {218 g, 2.84 equivalents) in klejnen portions at 80-104 ⁰ C to the mixture. 10 g of water are added and the resulting mixture is carbonized and ^{blown with nitrogen at 148 α} C for 2 hours and 20 minutes. It is filtered. The filtrate is heated to 165 ° C./12 mm Hg and the residue is diluted with xylene solution. The xylene solution has a Bariumsulfataschegehalt of 36.7% ^an d ^eme Rückflußbasenzahl of the 171st

The overbased metal salts prepared according to the above regulations prevent the deposition of sludge or paint-like substances in the engine in which the diesel oil is used. she also facilitate the combustion of diesel oil.

Diesel oils containing these overbased metal salts may contain other common additives, such as color stabilizers, antioxidants, rust inhibitors and dispersants. In many cases Diesel oils can contain 0.001 to about 2 percent by weight of one or more such additives. Specific Examples of such additives are metal-containing cleaning agents, such as barium didodecylbenzenesulfonate, the calcium salt of the hydrolyzed acidic product of polyisobutene with a molecular weight of 1000 and phosphorus pentasulfide, or magnesium mahogany sulfonate. Examples of other additives are tert-Dodecylamine and the imidazoline, which by reacting oleic acid with diethylenetriamine or Triethylenetetramine is obtained.

The overbased metal salts can be incorporated into diesel oils by mixing a desired amount of the additive with the diesel oil. You can also make a concentrate by dissolving the additive in a solvent such as xylene, toluene or mineral oil and then mixing the concentrate with the diesel oil. The concentrate can contain 5 percent by weight or less, or 90 percent or more of the solvent. The diesel oil usually contains up to about 5 ° / _0, usually from 0.1 to 2% of the additive.

The improved combustion properties of the diesel oils according to the invention are shown by a remarkably reduced tendency of the engine to form black exhaust smoke. These advantages are demonstrated by the following machine test, in which a single cylinder four-stroke diesel engine is operated with a compression ratio of 19: 1 under the following conditions: number of revolutions 1500 ± 10 rpm; Fuel consumption 1.2 ± 0.018 kg per hour; Machine load about 6 brake horsepower; Air-fuel ratio of about 19: 1, and oil sump temperature 55 ± 1.7 ⁰ C. The motor is equipped with a "smoke-tube" apparatus, for measuring the black exhaust Qualms, in which the exhaust gases pass through a glass tube having an outer diameter of 18 mm , in which the smoke is deposited on the inner wall of the pipe. The effectiveness of the additive in preventing black smoke formation is assessed by comparing the pipe with a set of standard pipes which have varying amounts of rainfall and are rated on a number scale from 0 to 10, with 0 no rainfall and 10 heavy rainfall indicates. The engine is also equipped with another device ("smoke spot" device) for measuring the black exhaust smoke, in which the exhaust gases pass through a white filter paper. The amount of black precipitate on the filter paper is also an indication of the effectiveness of the additive. The precipitate is scored in the same way by comparing the filter paper with a set of standard samples, ie papers which have different amounts of precipitation and are rated on a number scale from 0 to 10, with 0 indicating no precipitation and 10 indicating heavy precipitation. The fuel used is a common diesel oil with a sulfur content of 1 percent by weight. After a break-in period to establish equilibrium conditions, the engine is run on the diesel oil until the smoke stain rating is within the range of 8.5 to 9.0 and the smoke tube rating is within the range of 6.0 to 6.5. The engine is then run on the test fuel (produced by incorporating the additive into the diesel oil) until the operational equilibrium conditions are restored. The smoke tube rating and the smoke spot rating are recorded at the end of 15 and 30 seconds after equilibrium conditions have been reached. The results of the test are shown in Table I below.

Table I.

additive Weight percent Smoke stain rating 30 seconds Flue pipe evaluation 30 seconds of regulation in diesel oil 15 seconds 8.0 to 9.0 15 seconds | 5.5 to 6.5 none 7.0 to 8.0 4.0 5.5 1.0 A. 0.8 3.5 6.5 0.5 2.5 B. 0.34 5.0 6.5 2.0 3.0 C. 0.5 6.0 6.5 2.0 3.0 D. 0.5 5.5 6.5 2.0 2.5 E. 0.35 5.5 5.0 2.0 1.5 F. 0.35 4.0 4.5 1.5 1.5 G 0.35 3.5 6.5 1.5 3.0 H 0.35 5.0 3.0

Comparative tests: 65 A test engine is used in an intercity saddle

The comparison tests, the results of which were tractors installed four-stroke diesel engine with 12.18 1

in Table II are used as stroke volumes. The one with changing load

is carried out as follows: power transmitted to the drive wheels in each case

809 519/531

is determined by means of a dynamometer, with a constant engine speed of 1950 rpm is adhered to.

The already mentioned Rauchneck device is used to determine the exhaust smoke, which sucks a certain amount of exhaust gases through a filter paper disc with each measurement. The blackening of the soot spot left on the filter paper is determined by measuring the reflectivity of the soot stain photoelectrically. The review takes place in the manner already described

on a numerical scale from 0 to 10.

First of all, the so-called base oil, i.e. a diesel oil that does not reduce the development of soot, is used Additives, tested and then one after the other the diesel oils to be compared, which are produced by mixing the base oil are made with the various additives in appropriate proportions.

After each attempt, the fuel system is ίο completely flushed by first using the engine the base oil and then with the next diesel oil to be tested.

Table IT

Diesel oil

60

80

Load (hp)
100 I 120
Smoke stain value

140

Max.

Base oil 1

Base oil 2

1. German publication 1 071 867

2. German interpretation document 1071 867

3. U.S. Patent 2,781,403 ...

4. U.S. Patent 3,031,284 ...

5. Diesel oil X (according to the invention) ...

2.9

3.3

3.0 2.8

2.0

2.2

0.7

3.6
3.8

3.3
3.1

2.4
2.6

1.1

4.3 3.8

3.8

3.5

2.9

3.4

1.9

4.9
4.9

4.3 4.0

3.5
4.3

3.1

6.1 6.1

5.6

5.2

4.6 4.9

3.3

7.4 7.1

6.8 6.2

6.0 6.6

3.7

All additive quantities in percent by weight state the content of active additive, exclusively optionally through the production of solvents and / or diluents present in the additive (Mineral oil).

1. Diesel oil according to the German Auslegeschrift 1 071 867 (base oil 2, which per kilogram of oil per Contains 0.25 mg-atom of tin and lead in the form of sulfonates, corresponding to an additive content of about 0.05 percent by weight),

2. Diesel oil according to the German Auslegeschrift 1 071 867 (base oil 2, which per kilogram of oil per Contains 1 mg-atom of tin and lead in the form of sulfonates, which is an additive content of about 0.2 percent by weight),

3. Diesel oil according to US Pat. No. 2,781,403 (base oil 1 with a content of 0.06 percent by weight of an overbased barium salt according to Example 4 of this USA patent),

4. Diesel oil according to US Pat. No. 3,031,284 (base oil 1 with a content of 0.06 percent by weight an overbased barium petroleum sulfonate),

5. Diesel oil according to the invention (base oil with a content of 0.2 percent by weight of an overbased Barium salt according to regulation B).

As can be seen from the values in table Π, the diesel oils according to the invention are not only the Base oils, but also all known metal

superior to diesel oils containing compounds in terms of low smoke development.

Claims (1)

Claim: Low-smoke burning diesel oil containing an oil-soluble metal compound, thereby characterized in that it contains 0.1 to 5 weight percent of an oil soluble overbased metal salt contains that by treating a mixture of a) either one or more alkylated phenols with at least about 6 aliphatic ones Carbon atoms or from a mixture of a phenol and one or more polar ones Compounds having at least about 12 aliphatic carbon atoms selected from the group the esters of aliphatic carboxylic acids, sulphurized sperm oil, alcohols, sulfoxides, Amines and condensation products of amines with lower aliphatic aldehydes or with carboxylic acids and b) at least about 1 equivalent of an alkali or alkaline earth metal oxide or hydroxide with carbon dioxide, optionally in the presence of a mineral oil as a diluent and optionally in the presence of water. Documents considered: German Auslegeschrift No. 1 071 867; U.S. Patent Nos. 2,989,463, 2,971,014, 781,403, 3,031,284. 809 519/531 3. 68 © Bundesdruckerei Berlin